Resin and process for manufacturing the same from crude solvent naphtha.



.kinsburg, in the countyI UNITED STATES PATENT OFFICE.

IABG 11mm, 0 wnmsnum, PENNSYLVANIA, ASSIGNOR TO K. norms 66H- rm, or rmmsuvmn, A GOBPOBATIOH on rmmmvmu.

mm AID M95 FOB murnemma TB! 85!]! mm 01m 80km 1,297,328. P m Patented Mar. 18,1919. Ho Drewifl. application fled- Ssptembe: 8, 181.8. Serial I0. 2,9486.

To. all whom it my concern:

zen of the United States, residin at Wilof Alleg eny and State of Pennsylvania, ave. invented a new anld useful Improvement in Resins and Prooesses for Manufacturing the Same from Crude Solvent Naphtha, of which the following is a full, clear, and exam: description This invention relates to a new and. useful light colored resin and to the manufacture 0 the same from crude solvent naphtha ob.- tained from gas, tar, or petroleu-xns and is an improvement on the ordinary acid golynwrlzation rocess, as hereinafter Heretofore, inthe manufacture of resin by the acid pol erization process, the polymerization of e roan-forming constituents of crude solvent naphtha has been efiected by a sin le treatment or agitation with concentrate sulfuric. acid, fol owed by distillation. for the separation of the non-volatile resinified material from the non-resinified volatile oils. No provision is madein the qrdinary acid process for the seQaration of certain dark colored and injurious resinf orming constituents which occur in crude solvent naphtha, such as dicyclopenta fiene and styrolene. These substances are lyinerized very quickly to black ha comp unds by the autism of acid. 'Nei'thenof' these substances is desirable in a particularly when a light shade is required.

The object of this improvement and inethod of efiecting same is therefore as folows:

First, I 01 merize the dark resin-forming bodies by pgeliminary treatment with an acid of just suflicient strength to aecom lish this result without being strong enoug to polymerize either eoumerones or indenes or similar bodies to an appreciableextent.

Second, I distil the-partially washed sol; vent to-efleet the separation of the black resin-forming compounds which remain behind as a residue in the still, the nonpolymerized eoumarones and indenes dlstll- Iling over with the other volatile 0118 occurf in crude solvent naphtha.

ird, I com lately polymerize the coumarones and ones. in the distillate from the second ation by means of concentrated sulfuric acid, as in the case of ordinary acid polymerization process.

Fourth, neutralize any excess of sulfuric. aoid'loy agitation with a dilute solution of caustic s a or other alkaline agent. The resulting sulfate is drawn ofi in solution in the pgiileous layer. F1 1. separate the resin n the. thlrde ration from the v oil in which it is lssolved. Dram! 18* tlllation proees may be. employ d for this P orreeoursemaybeadvan. y, had to the blowing gmcess mention d in my Patent Np. 1,236, 1 for methmi of recovermg resm from benzol plant residues As a specific example of my method of tnt, I can use to advan sulfurie acid, and for the second a dash 0.4% by volume of 65 Baum sulfuric. mid. It is newbie to vary the per cents. and coneentration of the first, acid wash fairly large limits. The limitsof variation for the second wash are much narrower, and a poor quality of ream will be obtained ifiothe above figures are greatly ee med Al other proportions and methods of treatment mentioned in above ration are well known to those skilled in he art and need no further discussion The resin produced by my in ention is only lighter eolored than ordinary go d polymerized resin, but it is purer, praetlcall free, from pentadaene ami styr lew- T me ting point of my resin is intermcdlate between ordinary acid polymerized resin and the variety of heatrpolymerized resin known as yro parwoumaa'one resin 5. a, in the uni of 100 C. example of this resin 18 that b" the, process of the and Darrin P. lflo. 1,253,813 of April 23., 1916.; Its. solublllty in yarious organic liquids is greater than other resins produced from crude s lvent naphtha, and for this reason, it is preterable for the manufacture of ce tain tyses of varnishes and. otheroomposltions. hemically, my resin consists of practically pure ammum-erone and aeoumerone homofigues represented by the formula (0 0), and are indene represented by t e. formula (C, The initial acid wash practically trees this material from certain injurious substances such as polymerized dicomplished by a preliminary washing with a dilute caustic solution in the usual manner. Intermediate or final water washes or soda washes may be employed without departing from the essence of my invention; Likewise, various other changes may be made in the details of the operation of my invention, and it will be obvious to those skilled in the art that the same maybe modified in several ways without changing the operation or departing from my invention.

From the foregoing description of the invention, it will be clearly seen that I have.

devised a process particularly suitable for the production of light colored resins from crude solvent naphtha by means of special acid washing and double distillation" treatment. It can further be clearly seen that I have devised a process in which all the points set out in the statement of my invention are fully attained and carried out.

For a definition of some of the terms employed herein, reference may be had to atent 'No. 1,263,813, granted t F, W, Sperr, Jr., and myself on April 23, 1918.

Having: stated the nature and object of my invention and having described the method and procedure, what I desire to secure by Letters Patent is defined in the appended cl-aims.

I claim:

1. That step in the process of producing resin from a liquid containing compounds of the coumarone-indene group, which consists in initiall' treating the mixture with sulfuric acid 0 suilicient strength to polymerize dark resinforming bodies without appreciable polymerization of the contained coumarone-indene compounds. v

2., That step in the operation of producing resin from crude solvent naphtha, which consists in initially treating the crude solvent naphtha with sulfuric acid of suflicient strength 'to polymerize the contained dark resin-forming bodies without appreciably polymerizing the contained light resinorming compounds.

3. The steps in the process of producing resin from a liquid containing compounds of the coumarone-indene oup, which consist in initially treating .t e mixture with a solution of sulfuric acid of sufficient st-re to polymerize the contained dark resinformi g vconstituents without appreciably polymerizing the contained light resinforming constituents, subsequentl removing the dark resins by a distillation process, and then completing the polymerization of the light resin-forming compounds b treatment with a stronger solution of en furic'acid.

4. The steps in the process of lproducin resin from crude solvent napht a, whic consists in treating the crude solvent naphtha with a solution of sulfuric acid of suflicien't strength to polymerize the dark resin-fprmin constituents contained in the naphtha wit out appreciably polymerizing the light resin-forming constituents therein, subse uently removin the dark resin compoun s by a distillation process, and then completing the polymerization of the light resin-forming bodies by treatment with a. stronger solution of sulfuric acid.

5. he herein described process of producing resin from a liquid containing compounds of the coumarone-indene oup, comprising the steps of subjecting t e mixture secondary acid treatment, redistillin-g, and

, blowing a gaseous fluid through the residue to remote volatile oils from the polymerized resin.

6. The herein described process of producing resin from crude solvent naphtha, comprising the steps of subjecting the crude solvent naphtha to a rimary acid polymerization treatment, d istilling it, subjecting the distillate to a secondary acid treatment, redistilling, and blowing a gaseous fluid throulgh the residue toremove volatile oils from t e polymerized 7 The herein described process of produc ing resin from a liquid containing compounds of the coumarone-indene group, comprising the steps ofsirbjecting the mixture to an initial treatment with a solution of, sulfuric acid of suflicien't strength to.

polymerize the dark resin-forming constituents without an appreciable polymerization of the coumarone-ind'ene compounds, distilling the treated mixture 'for removal of dark resins, subjecting the distillate to a treatment with a stronger solution of sulfuric acid for the pn of lymerization of the coumarone-in ene bodi s, neutralizing any excess of acid, redistilling, and blowingla gaseous fiuid through the result ing lig t colored resin toremove volatil oilsfrom the polymerized. resin. 8. The herein described process of producing resin from crude solvent naphtha com prising the steps of subjecting the crude solvent naphtha to a primar acid treatment: with a solution of sul ric acid of suflicient strength to polymerize the dark resin-forming constituents without appreclably polymerizing the light resin-formi constituents, removing the, dark resinifi bodies by a distillation process, completing the polymerization of *the light resin-formin bodies by a treatment with a stronger SOfiltlOIl of'sulfuric acid, neutralizing any excess of anid, redistilling, and blowlng a seous fluid'through the'residue to remove volatile oils from thelymerization residue.

9. As a new artil of manufacture, a 1i ht colored resin produced from crude so vent naphtha. by acid pollymerization, but praetioally free from dieye opentadiene and st rolene, the melting point bein interme into between ordinary acid po ymerized resin and heat polymerized resin, that is, in the nei borhood of about 100 0., and its solu i'lity in most organic liquids being greater than'that of ordlnary resins rodueed from crude solvent naphtha.

10.- s a new article of manufaeture, a light colored resin produced from compounds of the ooumarone-indene group by acid polymerization process coupled with a dou ble distillation treatment, the resulting resin. being lighter in color and more soluble in most organic substances than ordinary acid polymerized paraeoumarone resin, the melting point being intermediate between that of ordinary polymerized paraooumarone and that of the varlety of heat-polymerized resin known as pyro-paraeoumarone resin, and being praetlealliy free from dieyclopentadiene and styro ene.

11. As a new article of manufacture, a

light colored resin consisting of praotieally pure perawoumarone and 1ts homologues, (C H O), and para indene (C HQ being praet-ioally free from polymerized dieyelopentadiene gC H and polymerized styrolene '(C H,

In testimony whereof, I have hereunto set my hand.-

MARC DARRIN.

should be read with these correctio It is hereby certified that inLettrs Patent N 0. 1,297,328, granted Marph 18, 1&19, upon the application of Marc D arrin, of Wilkinsburg, Pennsylvania, for an improvernent in Resins and Processes for Manufacturing the Same from Crude Solvent Naphtha, errors appear in the printed specification requiring correction as follows: Page 1, line 105, at end of formula, for the plus sign read z; page 2, line 2, before the formula insert a parenthesis; and that the said Letters Patent ns therein that the same may conform to the record of the case in the Patent Of fice.

Signed and sealed this 22d day of'June, A. D., 1920.

M. H. coULsToN,

Acting Commissioner of Patents.

[SEAL] D 1 SO LA I M E R 1,297,328.-Mara Darrin, Wilkinsburg, Pa. RnsrN AND Pnoozss' ma MANUFACTUR- nio THE SAME FROM CRUDE SOLVENT NAPHTHA. Patent dated March 18, 1919. Disclaimer filed May 23, 1924, by the assignee, The Koppers Company. Hereby disclaims initially treating a liquid containing compounds of the comma.- rone-indene group as specified in claim 1, except when followed by the separation of the polymerized dark resin-forming bodies from the liquid containing the unpolymerized coumarone-indene compounds and the subsequent treatment of such liquid with sulphuric acid so as to polymerize the ooumarone-indene compounds. Hereby disclaims initially treating the crude" solvent naphtha as specified in claim 2, except when followed by the separation of the polymerized dark resinforming bodies from the naphtha containing the unpolymerized light resin-forming compounds and the subsequent treatmentof such naphtha with sulphuricacid so as to polymerize the light resin-forming compounds.

Hereb disclaims the light colored resin as defined in claim 11. [Ofifcwl Gazette June 10, 1924.] 

